CN102816399A - PVDF (polyvinylidene fluoride) film modified with nano-titanium dioxide and preparation method for PVDA film - Google Patents
PVDF (polyvinylidene fluoride) film modified with nano-titanium dioxide and preparation method for PVDA film Download PDFInfo
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Abstract
The invention provides a PVDF (polyvinylidene fluoride) film modified with nano-titanium dioxide and a preparation method for the PVDA film. Fluorinated polyacrylate is grafted on the surface of the nano-titanium dioxide in the film, compatibility of TiO2 in PVDF is greatly improved due to the existence of a graft monomer, and when the PVDF film is used for solar cell back films, bonding force between the PVDF film and other dorsal plate base materials is greatly enhanced. The preparation method includes: firstly grating the fluorinated polyacrylate on the surface of TiO2, weighing graft copolymer and the PVDF according to a part ratio for mixing in a mechanical stirring manner, using an extruder for extrusion and strip formation after uniformly mixed, placing into a drying oven to dry moisture after being cut into granules, squeezing out by a single screw for tape casting, and obtaining the modified PVDF film.
Description
Technical field
The present invention relates to a kind of function film and preparation method thereof, particularly a kind of thin-film material that can be used for solar battery back film and preparation method thereof.
Background technology
The fluorine element electronegativity is big in the fluorine material on fluorine-containing notacoria surface; Van der Waals radius is little; The carbon-fluorine bond bond energy is extremely strong; And unique fluoridize tight, firm, the surface smoothing of volution rodlike molecule in the chain one-piece construction, make that each item performances such as weathering resistance, thermotolerance, lower temperature resistance and chemical proofing of fluoro-resin are very superior.Above-mentioned excellent properties makes when the notacoria that the fluorine material conduct takes blocking effect to outside atmosphere and inside solar energy battery, has improved the safety of long-term outdoor use.PVDF is a kind of semicrystalline polymer, and its second-order transition temperature is-39 ℃, and crystalline melt point is 160 ℃; Heat decomposition temperature is more than 316 ℃; Wherein the C-F key length is short, and bond energy is high, has extraordinary thermostability, erosion resistance and excellent uvioresistant performance.But the extremely strong C-F key of PVDF itself causes its surface hydrophilicity relatively poor; Therefore PVDF is if want to substitute the notacoria of traditional T PT as solar cell; Must improve its surface hydrophilicity; Improve the adhesiveproperties between itself and the backboard base material, carry out blending and modifying like multiple polymers such as PVDF and sulfonated polystyrene, PEG, TEB 3K, polyacrylonitrile, Yodo Sol VC 400, SPSFs.
Pvdf membrane is transparent relatively good simultaneously; In order to make it reach good shaded effect; In the process of producing, also need add a certain amount of white titanium pigment, the pvdf membrane for preparing plays reflex action to sunshine, also has good infrared emittance simultaneously; Reduce the working temperature of assembly, and then improve the service efficiency of assembly.Nanometer titanium dioxide has special performances such as higher specific surface energy, high reactivity, is widely used in aspects such as solar cell.But the particle diameter of nanometer titanium dioxide is very little, and specific surface area is big, surface energy is higher, is prone to take place agglomeration, forms offspring, and dispersion effect is not good in the PVDF matrix.Therefore, in the process that reality is used, need handle accordingly, improve its dispersive ability in PVDF white titanium pigment.Mention in " preparation of solar battery back film " literary composition titanium dioxide surface is carried out silane treatment, carry out blending and modifying with PVDF and PMMA, the part aggregation phenomenon appears in the titanium oxide for preparing in base material, and the mechanical property of material descends.
Patent CN 1667038A discloses PVDF and PMMA has been carried out blending and modifying, has prepared solar battery back film, improves the hydrophilicity of notacoria.But the adhesiveproperties between notacoria for preparing and the backboard base material still is poor, after through certain heat-resisting ageing-resisting test, and the phenomenon that can occur peeling off.The sun power backboard product of existing market main flow also need apply one deck sizing agent between pvdf membrane and backboard base material in the process of producing, solidify under certain conditions; Realize and the backboard base material between bonding; Like patent CN201387887Y, CN201387885Y etc., and the sizing agent that is adopted in the production process is a kind of solvent type, and environment is had certain pollution; Improved labor cost simultaneously, the process of production is more loaded down with trivial details.
Therefore, it is fine to develop a kind of and PVDF consistency, and simultaneously and the excellent a kind of new type solar energy notacoria material of the adhesiveproperties between the backboard base material, the novel PVDF notacoria material of realizing the successive suitability for industrialized production is a kind of inevitable trend.
Summary of the invention
The technical problem that the present invention will solve is: in the prior art; Adhesiveproperties between notacoria and the backboard base material is relatively poor, and during with white titanium pigment modification pvdf membrane, white titanium pigment is prone to take place agglomeration; Dispersion effect is not good in the PVDF matrix, and the mechanical property of material is descended.
For addressing the above problem, technical scheme provided by the invention is:
The invention provides the nano-titanium dioxide modified PVDF film of a kind of usefulness, the nano titanium oxide surface grafting in this film has the poly-fluorine-containing acrylic ester;
As preferably, in the film, the mass ratio of titanium oxide grafts and PVDF is: 10:90 ~ 30:70;
As preferably: the thickness of nano-titanium dioxide modified PVDF film is 25 ~ 40um;
As preferably, the particle diameter of nano titanium oxide is between 1 ~ 5um;
As preferably; Be grafted in the poly-fluorine-containing acrylic ester on nano titanium oxide surface; Fluorinated acrylate monomer is methylacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, methylacrylic acid 2; 2, a kind of or two kinds of mix monomers (the mix monomer ratio is between 1:1 ~ 1:2) in the 2-trifluoro ethyl ester;
As preferably: the concrete operations of nano titanium oxide surface grafting poly-fluorine-containing acrylic ester are: take by weighing reactant by ratio of quality and the number of copies, earlier to TiO
2Carry out silane treatment, washing, oven dry; With the TiO that handled
2Put into zero(ppm) water and be uniformly dispersed, add sodium hydroxide solution, mechanical stirring is warming up to 70 ~ 80 ℃ simultaneously; Feed nitrogen to remove the air in the reaction kettle; Begin to drip monomer after adding half initiator, drip off in 30 ~ 60min, behind reaction 1 ~ 2h; Add remaining half initiator, continue reaction 6 ~ 8h again; After reaction finishes, the vacuum filtration product, with drying behind the distilled water wash, technical process is as shown in Figure 1.
Further: the ratio of quality and the number of copies of reactant is 5 ~ 10 parts of nano titanium oxides; 5 ~ 10 parts of silane coupling agents; 50 parts ~ 100 parts of fluorinated acrylate monomers; 0.5 ~ 1.5 part of initiator.
The present invention also provides the preparation method of the nano-titanium dioxide modified PVDF film of a kind of above-mentioned usefulness; Concrete operations are: press ratio of quality and the number of copies weighing grafts and mix with PVDF, the blended mode is a mechanical stirring, after stirring; Forcing machine is extruded slivering; Dry after cutting into pellet, extrude flow casting molding, obtain modification PVDF film by single screw rod;
As preferably: ratio of quality and the number of copies is 10 parts ~ 30 parts of titanium oxide graftss; 70 parts ~ 90 parts of PVDF.
The invention has the beneficial effects as follows:
(1) TiO of process surface grafting
2In resin matrix, have good dispersiveness, avoided not passing through any surface-treated TiO
2Aggregation phenomenon takes place in resin matrix, and causes mechanical properties decrease;
(2) TiO
2Between ester group in the poly-fluorine-containing acrylic ester of surface grafting and the PVDF stronger hydrogen bond action is arranged, both consistencies are fine; Poly-fluorine-containing acrylic ester itself also has good weather and erosion resistance simultaneously; The PVDF film that obtains through modification has longer work-ing life (can reach more than 25 years) and other correlated performances, all is improved like hydrophilicity, resistance to elevated temperatures;
(3) in the PVDF film that modification obtains, the poly-fluorine-containing acrylic ester and PET, polyolefins and the nylon that contain have bond effect preferably, have solved between present pvdf membrane and other backboard base materials problems such as cohesive force is weak.
The present invention be a kind of novel solar battery backboard that need not use sizing agent with modification PVDF film, the preparation method is simple, feasibility is good, but continuous industry production has higher percentage of grafting, has reduced pollution.
Description of drawings
The flow process of Fig. 1 nano titanium oxide surface grafting poly-fluorine-containing acrylic ester
Conventional nano titanium oxide and surface grafting have the infrared spectrogram of the nano titanium oxide of poly-fluorine-containing acrylic ester in Fig. 2 specific embodiment 1.
Embodiment
Embodiment 1:
Nano-TiO
2The preparation method of surface grafting poly-fluorine-containing acrylic ester is specially: in reaction kettle, add dry 10 parts of good nano-TiOs successively
2(particle diameter is 1um), the γ-An Bingjisanyiyangjiguiwan of 100 parts YLENE and 5 parts, mechanical stirring 8h.After reaction finishes, filter absolute ethanol washing, vacuum-drying.Take by weighing 8 parts of nano-TiOs through silane treatment
2Place reaction kettle; Add 100 parts zero(ppm) water, the sodium hydroxide solution of 5 parts of 0.5mol/L successively; Mechanical stirring slowly is warming up to 70 ℃, feeds nitrogen to remove the air (time is about 30min) in the reaction kettle, adds 0.25 part ammonium persulphate; The methylacrylic acid ten difluoro heptyl esters (dripping off in the 30min) of 0 part of Dropwise 5 slowly simultaneously are behind the reaction 2h.Add remaining 0.25 part ammonium persulphate, continue reaction 8h, after reaction finishes, vacuum filtration product, distilled water wash several, oven dry.
Fig. 2 has the infrared spectrogram of the nano titanium oxide of poly-fluorine-containing acrylic ester for conventional nano titanium oxide and surface grafting; Two curves are respectively the ir spectra of the titanium oxide of titanium oxide and graft modification among the figure; From figure, can significantly observe modification titanium oxide later and new absorption peak occur; Wherein, 2916.24cm
-1, 2848.73cm
-1Be CH
2Stretching vibration peak, 1702.63cm
-1Be the stretching vibration peak of C=O, 1463.87cm
-1Be the flexural vibration of C-H, but owing to there being the strong fluorine of electronegativity skew to occur above the carbon atom that closes on, from scheming upward at 990cm
-1More weak absorption peak appears in the place, is the absorbed oscillation peak of C-F key.Therefore, can from Fig. 2, draw, in the titanium dioxide surface grafting fluorine-containing XPA.
Press quality than 10 parts of TiO of weighing
2Grafts mixes with 90 parts of PVDF, and the blended mode is a mechanical stirring, and stir speed (S.S.) is 100 rev/mins, and the time is 5 minutes.Forcing machine extruding pelletization then, extrude parameter and be:
Table 1 forcing machine granulation parameter
| One district | Two districts | Three districts | Four districts | The mouth mould | Screw speed |
| 130℃ | 160℃ | 180℃ | 200℃ | 190℃ | 40r/min |
Place baking oven to dry by the fire 6h down for 80 ℃ the pellet of making, extrude flow casting molding by single screw rod, curtain coating obtains modification PVDF film (gauge control is at 25um).
Table 2 film casting temperature
| One district | Two districts | Three districts | Four districts | The mouth mould | Screw speed |
| 150℃ | 170℃ | 190℃ | 210℃ | 180℃ | 20r/min |
Embodiment 2:
Nano-TiO
2The preparation method of surface grafting poly-fluorine-containing acrylic ester is specially: in reaction kettle, add dry 10 parts of good nano-TiOs successively
2(particle diameter is 5um), the γ-An Bingjisanyiyangjiguiwan of 100 parts YLENE and 10 parts, mechanical stirring 9h.After reaction finishes, filter absolute ethanol washing, vacuum-drying.Take by weighing 8 parts of nano-TiOs through silane treatment
2Place reaction kettle; Add 100 parts zero(ppm) water, the sodium hydroxide solution of 5 parts of 0.5mol/L successively; Mechanical stirring slowly is warming up to 70 ℃, feeds nitrogen to remove the air (time is about 30min) in the reaction kettle, adds 0.5 part ammonium persulphate; Drip simultaneously 75 parts dodecafluorhe-ptylacrylate (dripping off in the 45min) slowly, behind the reaction 2h.Add remaining 0.5 part ammonium persulphate, continue reaction 8h, after reaction finishes, vacuum filtration product, distilled water wash several, oven dry.
Press quality than 20 parts of TiO of weighing
2Grafts mixes with 80 parts of PVDF, and the blended mode is a mechanical stirring, and stir speed (S.S.) is 100 rev/mins, and the time is 5 minutes.Forcing machine extruding pelletization then, extrude parameter and be:
Table 3 forcing machine granulation parameter
| One district | Two districts | Three districts | Four districts | The mouth mould | Screw speed |
| 130℃ | 160℃ | 180℃ | 200℃ | 190℃ | 40r/min |
Place baking oven to dry by the fire 6h down for 80 ℃ the pellet of making, extrude flow casting molding by single screw rod, curtain coating obtains modification PVDF film (gauge control is at 30um).
Table 4 film casting temperature
| One district | Two districts | Three districts | Four districts | The mouth mould | Screw speed |
| 150℃ | 170℃ | 190℃ | 210℃ | 180℃ | 20r/min |
Embodiment 3:
Nano-TiO
2The preparation method of surface grafting poly-fluorine-containing acrylic ester is specially: in reaction kettle, add dry 7.5 parts of good nano-TiOs successively
2(particle diameter is 2.5um), the γ-An Bingjisanyiyangjiguiwan of 100 parts YLENE and 10 parts, mechanical stirring 9h.After reaction finishes, filter absolute ethanol washing, vacuum-drying.Take by weighing 8 parts of nano-TiOs through silane treatment
2Place reaction kettle; Add 100 parts zero(ppm) water, the sodium hydroxide solution of 5 parts of 0.5mol/L successively; Mechanical stirring slowly is warming up to 70 ℃, feeds nitrogen to remove the air (time is about 30min) in the reaction kettle, adds 0.35 part ammonium persulphate; Simultaneously the vinylformic acid hexafluoro butyl ester of 0 part of Dropwise 5 and 50 parts methylacrylic acid hexafluoro butyl ester (dripping off in the 60min) slowly are behind the reaction 2h.Add remaining 0.35 part ammonium persulphate, continue reaction 8h, after reaction finishes, vacuum filtration product, distilled water wash several, oven dry.
Press quality than 30 parts of TiO of weighing
2Grafts mixes with 70 parts of PVDF, and the blended mode is a mechanical stirring, and stir speed (S.S.) is 100 rev/mins, and the time is 5 minutes.Forcing machine extruding pelletization then, extrude parameter and be:
Table 5 forcing machine granulation parameter
| One district | Two districts | Three districts | Four districts | The mouth mould | Screw speed |
| 130℃ | 160℃ | 180℃ | 200℃ | 190℃ | 40r/min |
Place baking oven to dry by the fire 6h down for 80 ℃ the pellet of making, extrude flow casting molding by single screw rod, curtain coating obtains modification PVDF film (gauge control is at 40um).
Table 6 film casting temperature
| One district | Two districts | Three districts | Four districts | The mouth mould | Screw speed |
| 150℃ | 170℃ | 190℃ | 210℃ | 180℃ | 20r/min |
More than the test of each embodiment performance of products, as shown in table 7:
The test of table 7 embodiment 1,2,3 properties of sample
| Test event | Measuring unit | Unmodified PVDF | 1 | 2 | 3 |
| Contact angle | ° | 91.146 | 58.20 | 58.31 | 59.63 |
| Film thickness | um | 25 | 20 | 30 | 40 |
| Interlaminar strength | N/cm | 9 | 12.6 | 12.8 | 11.9 |
| PCT（50h） | ? | Xanthochromia | Xanthochromia not | Xanthochromia not | Xanthochromia not |
| Tensile strength | Mpa | 23 | 32.2 | 31.9 | 33.0 |
Wherein PCT is the high temperature accelerated weathering test.(wherein interlaminar strength be meant the double layer material that carries out between PVDF and the PET after multi-layer co-extruded test the result who obtains).
Claims (9)
1. one kind with nano-titanium dioxide modified PVDF film, and it is characterized in that: described nano titanium oxide surface grafting has the poly-fluorine-containing acrylic ester.
2. modification PVDF film as claimed in claim 1 is characterized in that: in the described nano-titanium dioxide modified PVDF film, the mass ratio of titanium oxide grafts and PVDF is: 10:90 ~ 30:70.
3. modification PVDF film as claimed in claim 1 is characterized in that: the thickness of described nano-titanium dioxide modified PVDF film is 25 ~ 40um.
4. modification PVDF film as claimed in claim 1 is characterized in that: described nano titanium oxide particle diameter is 1 ~ 5um.
5. modification PVDF film as claimed in claim 1; It is characterized in that: described being grafted in the surperficial poly-fluorine-containing acrylic ester of nano titanium oxide; Fluorinated acrylate monomer is methylacrylic acid ten difluoro heptyl esters, dodecafluorhe-ptylacrylate, vinylformic acid hexafluoro butyl ester, methylacrylic acid hexafluoro butyl ester, methylacrylic acid 2; 2, a kind of or two kinds of mix monomers in the 2-trifluoro ethyl ester.
6. modification PVDF film as claimed in claim 1 is characterized in that the concrete operations of described nano titanium oxide surface grafting poly-fluorine-containing acrylic ester are: take by weighing reactant by ratio of quality and the number of copies, earlier to TiO
2Carry out silane treatment, washing, oven dry; With the TiO that handled
2Put into zero(ppm) water and be uniformly dispersed, add sodium hydroxide solution, mechanical stirring is warming up to 70 ~ 80 ℃ simultaneously; Feed nitrogen to remove the air in the reaction kettle; Begin to drip monomer after adding half initiator, drip off in 30 ~ 60min, behind reaction 1 ~ 2h; Add remaining half initiator, continue reaction 6 ~ 8h again; After reaction finished, the vacuum filtration product was with drying behind the distilled water wash.
7. the preparation method of nano titanium oxide surface grafting poly-fluorine-containing acrylic ester as claimed in claim 6, it is characterized in that: the ratio of quality and the number of copies of described reactant is: 5 ~ 10 parts of nano titanium oxides; 5 ~ 10 parts of silane coupling agents; 50 parts ~ 100 parts of fluorinated acrylate monomers; 0.5 ~ 1.5 part of initiator.
8. like the preparation method of each described modification PVDF film of claim 1 to 7; It is characterized in that concrete operations are: press ratio of quality and the number of copies weighing grafts and mix with PVDF, the blended mode is a mechanical stirring, after stirring; Forcing machine is extruded slivering; Dry after cutting into pellet, extrude flow casting molding, obtain modification PVDF film by single screw rod.
9. the preparation method of modification PVDF film as claimed in claim 8 is characterized in that: described ratio of quality and the number of copies is: 10 parts ~ 30 parts of titanium oxide graftss; 70 parts ~ 90 parts of PVDF.
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Cited By (8)
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| CN103130968A (en) * | 2013-03-12 | 2013-06-05 | 南京理工大学 | Low-surface-free-energy TiO2 nano composite particles and preparation method thereof |
| CN104474931A (en) * | 2014-12-04 | 2015-04-01 | 天津大学 | Preparation method of modified polyvinylidene fluoride hybrid film and application thereof |
| CN104857866A (en) * | 2015-05-18 | 2015-08-26 | 上海交通大学 | Method for preparing hydrophilic modified polyvinylidene fluoride membrane |
| CN105001564A (en) * | 2015-07-23 | 2015-10-28 | 哈尔滨工业大学 | Method for preparing dielectric film of high-energy-storage capacitor |
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| CN102179920A (en) * | 2011-04-06 | 2011-09-14 | 中山大学 | Method for preparing high-strength polymer composite material |
| CN102432963A (en) * | 2011-08-17 | 2012-05-02 | 常州荣晟新材料科技有限公司 | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film |
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| CN102134359A (en) * | 2011-01-07 | 2011-07-27 | 东华大学 | Solar cell back film and preparation method thereof |
| CN102179920A (en) * | 2011-04-06 | 2011-09-14 | 中山大学 | Method for preparing high-strength polymer composite material |
| CN102432963A (en) * | 2011-08-17 | 2012-05-02 | 常州荣晟新材料科技有限公司 | Fluorinated weather-resistant film for solar photovoltaic battery back plate and preparation method of fluorinated weather-resistant film |
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| CN103130968A (en) * | 2013-03-12 | 2013-06-05 | 南京理工大学 | Low-surface-free-energy TiO2 nano composite particles and preparation method thereof |
| CN104474931A (en) * | 2014-12-04 | 2015-04-01 | 天津大学 | Preparation method of modified polyvinylidene fluoride hybrid film and application thereof |
| CN104474931B (en) * | 2014-12-04 | 2016-03-23 | 天津大学 | A kind of preparation method of Kynoar hybridized film of modification and application thereof |
| CN104857866A (en) * | 2015-05-18 | 2015-08-26 | 上海交通大学 | Method for preparing hydrophilic modified polyvinylidene fluoride membrane |
| CN105001564A (en) * | 2015-07-23 | 2015-10-28 | 哈尔滨工业大学 | Method for preparing dielectric film of high-energy-storage capacitor |
| CN106497286A (en) * | 2016-10-26 | 2017-03-15 | 中国人民解放军空军勤务学院 | A kind of metal anti-corrosive paint |
| CN106497345A (en) * | 2016-10-26 | 2017-03-15 | 中国人民解放军空军勤务学院 | A kind of metal anticorrosive paint |
| CN107312277A (en) * | 2017-07-14 | 2017-11-03 | 常州回天新材料有限公司 | The weather-proof polyvinylidene difluoride film raw material and its manufacture method of high adhesiveness |
| CN112167490A (en) * | 2020-09-08 | 2021-01-05 | 杭州贝聪美健康科技有限公司 | Production process of fructose malt carbohydrate beverage |
| CN112167490B (en) * | 2020-09-08 | 2023-04-07 | 杭州贝聪美健康科技有限公司 | Production process of fructose malt carbohydrate beverage |
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